FR2497208A1 - MULTI-COMPONENT POLYMER RUBBER - Google Patents

Abstract

THE INVENTION RELATES TO A MULTI-COMPONENT POLYMERIC RUBBER; IT IS COMPOSED OF A 15 TO 60 MOLES OF AN A, B-INSATURE, B NITRILE 10 TO 75 MOLES OF A CONJUGATED DIENE AND C 2 TO 55 MOLES OF AN ACRYLATE OR METHACRYLATE OF FLUOROALKYL OR OF AN A-OLEFINE FLUORINE AND IT HAS A GLASS TRANSITION TEMPERATURE T OF -50C TO -20C, THE PERCENTAGES OF COMPONENTS A, B AND C BEING EXPRESSED IN RELATION TO THE TOTAL SUM OF THE MOLES OF COMPONENTS A, B AND C; THIS MULTI-COMPONENT POLYMERIC RUBBER SHOWS EXCELLENT RESISTANCE TO ACIDIC GASOLINE AND TO GASOLINE CONTAINING ALCOHOL.

Description

i

  The present invention relates to a poly-

mother with several components.

  More particularly, the invention relates to a new

  polymer calf made of a 3-unsaturated nitrile X, a conjugated diene and a fluoroalkyl acrylate or methacrylate and / or a fluorinated -4-olefin, which is particularly useful as a rubbery material contact with fuels. In recent years, automobile exhaust regulations have become strict and each car manufacturer has taken appropriate action;

  however, there is a new problem which is the forma-

  tion of acidic essence (this term designates an essence containing

  peroxides formed by the oxidation of gasoline at temperatures

  high erasures, which is described in detail by A. Nersasian, in Rubber and Plastics News, June 26 (1978)) during the

walking cars.

  As the crude oil market is tight around the world, attempts have been made to mix alcohol with gasoline. As a rubbery material coming into contact with

  fuels, we have generally used a rubber to date

  butadiene-acrylonitrile cabbage; however such a ma-

  does not resist acid gasoline and gasoline

above mentioned alcohol.

  As a method of remedying this defect, resistance to acid gasoline can be improved by using a mixture of butadiene rubber and acrylonitrile and vinyl chloride (published patent application unexamined JA 89338/80). However this mixture is inferior by other physical properties than a rubbery material coming

  contact with fuels must possess, such as re-

  resistance to low temperatures, slight deformation

  manente by compression and the like and it is desirable to remedy this defect. We have highlighted the interest of fluorinated rubber as a rubbery material resistant to contact with fuels because it has excellent

  resistance to acidic petrol and petrol containing al-

  cool above (see Tsuyoshi Sugimoto of Showa Neoplene Co., Ltd., "Request for Fluororubber" Viton "of the Recent Automobile Industry" which is a document of "Lecture Meeting for

  Introduction of Tokai Branch of the Rubber Society of Japan ".

  However, fluorinated rubber is not vulcanizable at

  sulfur, its properties after vulcanization without aging-

  are bad, it is difficult to handle and very

  expensive and therefore cannot usually be used

  read as a rubbery material coming into contact with

fuels.

  The Applicant has therefore carried out im-

  bearing on materials having an excellent resistance to acid gasoline and to gasoline containing alcohol, which is vulcanizable with sulfur and which one can easily use like rubbery materials coming into contact with fuels by use of a conventional molding apparatus and technique and discovered that the desired new material can be produced by copolymerization

  a nitrile o ', P-unsaturated, a conjugated diene and an acry-

  late or fluoroalkyl methacrylate and / or a fluorinated o-olefin. The invention therefore provides a polymer rubber to

  several components comprising (A) 15 to 60 mole% of a ni-

  trile o, P-unsaturated, (B) 10 to 75 moles F of a conjugated diene

  ford and (C) 2 to 55 mol% of a fluoroalkyl acrylate or methacrylate and / or of a fluorinated df -olefin, and which has a glass transition temperature (Tg) of -50 to -20 C, the percentages components (A), (B) and (C) being expressed relative to the sum of the moles of components (A), (B) and (C).

  Examples of c, p-unsaturated nitriles, i.e.

  say of component (A) used in the invention are the acryl-

  lonitrile, 1 '- -chloroacrylonitrile, 1' l -fluoroacryloni-

  trile, methacrylonitrile, ethacrylonitrile and the like.

  Among them, acrylonitrile is particularly preferred.

  The conjugated diene (B) used in the invention

  includes, for example, 1,3-butadiene, 2-chloro-1,3-bu-

  tadiene, 2-fluoro-1,3-butadiene, 2-methyl-1,3-buta-

  diene and the like. Among them we particularly prefer

l, 3-butadiene.

  Fluoroalkyl acrylate or methacrylate (C) u-

  used in the invention preferably has 1 to 20 carbon atoms and better still 1 to 15 carbon atoms in the alkyl radical and mention may be made, for example, of ll-dihydroperfluoroethyl acrylate or methacrylate, acrylate or methacrylate of ll-dihydroperfluoropropyl, 1,1,5-trihydroperfluorohexyl acrylate or methacrylate, acrylate

  or 1,1,2,2-tetrahydroperfluoropropyl methacrylate, a-

  3,1,7-trihydroperfluoroheptyl crylate or methacrylate, 1,1-dihydroperfluorooctyl acrylate or methacrylate, 1,1-dihydroperfluorodecyl acrylate or methacrylate and

  similar. Among them we particularly prefer lacryla-

  te or 1,1-dihydroperfluoroethyl methacrylate and acryl-

  late or 1,1-dihydroperfluoropropyl methacrylate.

  The fluorinated --olefin (C) comprises for example the

  vinylidene fluoride, tetrafluoroethylene, chloro-

  trifluoroethylene, dichlorodifluoroethylene, hexafluoro-

  propylene, 1,1,1-trifluoropropylene, l-hydropentafluo-

  ropropylènz and the like. Among them we particularly prefer

  chlorotrifluoroethylene and / or dichlorodifluoro-

  ethylene. We can use acrylate or methacrylate

  fluoroalkyl and 1-fluorinated l-olefin separately -or in combination

naison.

  In the polymer of the invention, the proportions of components (A), (B) and (C) expressed relative to the total sum of their moles are as follows: component (A), 15 to 60 mole%, preferably 20 to 55 mole% and better

  20 to 45 mole%; component (B), 10 to 75 mol%, preferably

  20 to 75 mol% and better still 30 to 70 mol%; and component (C), 2 to 55 mol%, preferably 2 to 45 mol 7o and better still 2 to 35 mol No.

  When the proportion of component (A) in the po-

  lymer is less than 15 mole% o, the polymer has a lower resistance to solvents and when it is greater than 60 mole%, the polymer becomes resinous and not only its ability to process but also its

  resistance to low temperatures are lower.

  When the proportion of component (B) is less

  less than 10 mole%, the elasticity of the rubber is lower

  re and the properties of the vulcanizate without aging are not satisfactory and when it is greater than 75

  5o moles, the polymer is inferior from the point of view of its

  resistance to solvents, its resistance to petrol containing

  alcohol and its resistance to acidic essence.

  When the proportion of component (C) is less

  less than 2 mole%, there is no effect on the resistance to acid gasoline and the resistance to gasoline containing

  alcohol and when it is greater than 55 mole%, the re-

  resistance to low temperatures of the polymer is lower.

  The glass transition temperature (T) of said copolymer is from -50 to 20 OC and when the T of such

  polymer composition drops below -50 OC, re-

  the oil resistance of the copolymer is not satisfactory,

  while when it rises above -20 OC, the re-

  resistance to low temperatures of the copolymer is not

satisfying.

  The polymer of the invention is produced by polymer

  radicalization and the polymerization process can be any known general polymerization process, including bulk polymerization, solution polymerization, emulsion polymerization and suspension polymerization, into which the monomer can be added and

  other components discontinuously, continuously or intermittently

  termittent to synthesize the polymer.

  As a radical polymerization initiator, conventional radical catalysts can be used, such as peroxides, redox catalysts, persulfates and azo compounds. With regard to the polymerization temperature, polymerization is possible in a range of temperatures from 5 to 80 ° C. although the

range from 5 OC to 60 OC.

  The polymer obtained according to the above-mentioned reaction can be recovered in the form of an elastomer according to a conventional coagulation process using a metal salt such as

  calcium chloride or the like or a method of coagula-

  tion using a non-solvent such as ethanol,

methanol or the like.

  The multi-component polymer produced according to

  the invention can be solid or liquid depending on the use

  wise. The molecular weight of the terpolymer has no limita-

  strict tion although its Mooney viscosity (MLi + 4, 100 0C)

  preferably 30 to 150 when copoly-

solid mother.

  If necessary, the polymer can be incorporated

  re to several components of the invention one or more a-

  conventional mixing gents, such as vulcanizing agents

  sation, vulcanization accelerators,

  reinforcement, fillers, plasticizers, scavengers

  softeners, antioxidants, stabilizers, blowing agents and the like and can be easily vulcanized by a conventional vulcanization process. The vulcanizing agents can be freely chosen from the vulcanizing agents generally used for rubber, such as those of sulfur type, of thiuram type, of peroxide type.

organic and the like.

  Like conventional butadiene-acrylic rubbers

  lonitrile, it is also possible, if necessary, to mix the polymer with several components of the invention with

  polyvinyl chloride or the like.

  By vulcanization, the polymer has several components

  sants of the invention provides an ex vulcanization product

  due to its tensile strength, without elongation,

  its resistance to low temperatures, its resistance to

  sence containing alcohol, its resistance to acidic essence and its resistance to oil and having a low permanent deformation by compression. So this copolymer can be used favorably as a rubbery material coming from

in contact with various fuels.

  The invention is explained in more concrete terms by

  the illustrative but in no way limiting examples below.

  In the examples and comparative examples, the parts

  are expressed by weight unless otherwise indicated.

  Examples 1 to 5 and comparative examples 1 to 8.

  A polymerization is carried out at 50 ° C. in an au-

  toclave with a capacity of 6 liters, using the mo-

  names and the polymerization agents listed below: Acrylonitrile 1,3-butadiene 100 parts Acrylate or methacrylate (see fluoroalkyl table 1)) Water 200 parts Soap of alkylsulfate type 5 parts Potassium phosphate 0.2 part Tert-dodecanethiol see table FeSO4.7H20 OO0 part Trisodium salt of ethylenediaminetetraacetic acid O, 020 part Sodium formaldehyde sulfoxylate 0.08 part P-menthane hydroperoxide 0.06 part

  When reaching the conversion of polymerization

  tion indicated in table 1, 0.2 part of hy-

  droquinone per 100 parts of the monomers to stop the polymerization. Then the mixture obtained is heated, the residual monomers are removed under reduced pressure and then 1.5 parts of an antioxidant consisting of phosphite are added to the residue.

  of allyl alkylated per 100 parts of dry matter of the rubber

  cabbage and the latex is coagulated with an aqueous solution of calcium chloride. The lumps obtained are washed with water and then dried under reduced pressure at 50 ° C. to prepare a sample for evaluation. The Mooney viscosity, the composition of the copolymer and the glass transition temperature of each of the samples thus obtained are shown

in table 1.

  The infrared absorption spectrum of the polymers has an absorption band characteristic of a C = N bond at 2,200 cm-1 and a C = O bond of an ester at 1,760 --1 cm, as well as '' a characteristic absorption band of a

  HC bond = CH cis at 970 cm 1 The measurement of T by ana-

g

  differential thermal lysis shows that each of the polymers

  res at a single glass transition temperature appearing

  in Table 1 which indicates that it is a copolymer.

  Determination of the characteristics of the vulcanization product.

  With each of the copolymers appearing in the ta-

  1, compositions are prepared according to the formula below

  under and they are vulcanized at 160 C for 15 minutes.

  Polymer formula 100 parts Zinc oxide 5 parts Stearic acid 1 part Carbon black: MTCB (carbon black 70 parts in a medium oven) Sulfur 0.5 part Tr accelerator (tetramethylthiuram disulfide) 1.8 parts

CZ accelerator (N-cyclohexyl-2-

  benzothiazole sulfenamide) 2.0 parts The characteristics of the products are determined.

  vulcanization thus obtained according to the method of standard ja-

  ponaise JIS K 6301. Their resistance to acid gasoline and their resistance to gasoline containing alcohol is evaluated.

according to the following methods.

  Method for evaluating resistance to acid gasoline.

  The term "a cycle" by definition means the im-

  immersion of each of the samples in a solution of 1 g of lauroyl peroxide in 99 g of Fuel C (mixed solvent

  consisting of a mixture in equal volumes of isooctane and to-

  luene) at 80 C for 24 hours, and each sample is submitted

  three immersion cycles and then dried under pressure

  sion reduced to 160 C for 15 hours before determining the elongation at cracking and the elongation at break according to the JIS K 6301 method, which constitutes an evaluation

  resistance to acidic gasoline.

  Gasoline resistance assessment method

containing alcohol.

  We assess the resistance to gasoline containing

  alcohol by LV measurement after immersion of each of the

  samples in a solution consisting of a 20/80 mixture

  methanol and Fuel C at 40 C for 48 hours.

  The results of the evaluation appear in the ta-

beau 2.

  As shown in Table 2, the ternai-

  re of the invention constitutes a rubbery material for

  before coming into contact with fuels and having characteristics

well balanced teristics.

  Examples 6 to 9 and comparative examples 9 to 13

  A polymerization is carried out at 50 ° C. in an au-

  toclave with a capacity of 6 liters using mono-

  mothers and the polymerization agents indicated below: Acrylonitrile 100 parts 1,3-butadiene (see fluorinated 0-olefin) table 3) K2S208 0.3 part fatty acid soap 5.0 parts Tert-dodecanethiol see table at

  When each of the po-

  lymerization indicated in table 3, 0.2 is added per

  hydroquinone tie for ioe parts of the monomers for arresting

ter polymerization.

  Then, the mixture obtained is heated, the residual monomers are removed under reduced pressure, an antioxidant consisting of alkylated allyl phosphite is added to the residue at a rate of 1.5 parts per 100 parts of dry matter of the rubber and the latex is coagulated with an aqueous solution of calcium chloride. The lumps obtained are washed with water and then dried under reduced pressure at 50 ° C. to prepare a sample for evaluation. The Mooney viscosity, the composition of the copolymer and the glass transition temperature of each of the samples thus obtained

are shown in Table 3.

  The infrared absorption spectra of the polymer

  have an absorption band characteristic of a bond

  its C = N at 2200 cm1, of a C-F connection between 1250 and -l -l

  1150 cm and an HC = CH cis link at 970 cm-

  The measurement of the glass transition temperature (T) by differential thermal analysis shows that each of the polymers has a unique T whose value is given in the

  Table 3 which indicates that it is a copolymer.

  Determination of the characteristics of the vulcanization product.

  With each of the copolymers appearing in the ta-

  bleau 3 we prepare compositions having the same formula as

  in Example 1 and vulcanized at 160 OC for 15 minutes.

  The characteristics of the vulcanization products thus obtained are evaluated as in Example 1. The results of

  the assessment is shown in Table 4.

  As shown in Table 4, the copolymer ter-

  naire of the invention constitutes a rubbery material which can come into contact with fuels and having

  well-balanced characteristics.

TABLE 1

  Monomers used (parts) Tert-dodecane-

Thiol acrylate, set

work (by-

  Butadiene Acrylonitrile fluoroalkyle ties) Exem-f Ople * 1)

1 20 25 55 0.30

2 38 32 30 * 1) 0.41

"3 15 35 60 * 3) 0.41

"4 27 44 29 * 2) 0.40

"5 14 50 36 * 4) 0.50

Compap rative example * 1)

1 62 8 30 0.08

"2 60 40 0 0.33

* 1)

3 63 32 5 0.45

4 50 40 10 * 2) 0.55

55 25 20 * 3) 0.30

-,, -

"6

"6 30 20 50 * 2) 1 0.30

"7 6 81 13 * 2) 1.00

"8 9 23 68 * 2) 0.30

  TABLE 1 (continued) Viscosity 'Conver- Mooney Composition of the copolymer (o molar) * 5) sion of 1000C polymer (l1 + 4 Acrylate of final sation (b) tButadiene Acrylonitrile fluoroalkyle

, 3 65 49 33 18

63.3 36.5 59 34 7

62.4 46.0 56 35 9

, 0 55 40 35 25

59.0 65 30 40 30

61.5 70.5 86 7 7

71.0 70 60 40 0

68.0 56 64 35 1

, 0 71 47 49 4

59.5 77 75 22 3

61.0 70 50 10 40

58.0 - 20 70 10

, 0 66 20 20 60

  ,, TABLE 1 (continued) Intense transition temperature Tg (OC) -27 -28 26 -22 -21 -60 -22 -38 -15 -55 -42 +47 -6 Note: * 1) Acrylate is used

1,1-dihydroperfluoro-

  propyl * 2) -We use acrylate

1,1-dihydroperfluoro-

  ethyl * 3) We use acrylate

1,1,7-trihydroperfluoro-

  heptyle * 4) We use acrylate

1,1-dihydroperfluoro-

  butyl * 5) Method of analysis of the composition of the copolymer,

a) Determination of a-

fluoroal crylate-

kyle by closed combustion

b) Determination of nitri-

the J, P-unsaturated according to

Kjeldahl's method.

TABLE 2

  Example 1 Example 2 Example 3 ..., _ Physical properties of the vulcanizate Resistance to tractign 147 109 135 (daN / cm) Elongation (%) 420 430 460 Hardness (JIS-A) 66 64 64

AT,,. .,

  Resistance to petrol containing alcohol

AV (,) 50.2 60.2 59.5

* Resistance to petrol

acid. .

  Elongation at the Pas de Pas de Pas of cracking (%) fissura- fissurafissuration tion Elongation at break (%) 315 255 290 Resistance to solvent Fuel C SV after immersion 27.6 32.1 30.1 to 40 C for 48 h (%) Low temperature resistance test Fragility test -24.2 2 impact (C) -25.2 23 Permanent compression deformation (%) 22 25 24 C x 70 h Note: In Comparative Example 7 , the product is resinous

  and therefore we cannot determine the properties.

  TABLE 2 (continued) Example 4 Example 5 Example E pe and comparative 1comparative 3

157 177 118 134 130

370 340 480 460 450

72 75 65 63 67

41.2 30.5 111 76.0 80.0

  Pas de Pas de Pas de 50 80 fissurati nfissura-fissuratio 5 tion

280 300 220 160 165

, 8 15.2 86.0 39.0 50.0

I - _ _

-21.5 -20.2 -47 -24.2 -27.8

  27 29 12 i24 23 TABLE 2 (continued) Example com Example com Example com Example example com Example

  parative 4 parative 5 parative 6 parative 7 comparative

_._ _tif 8

390 410 210 - 175

69 65 80 - 65

52.0 90.0 90.2 - 56.8

  | 150 No - No tion l J issuration fsua

205 I 185 190 160

.2 67.0 43.8 - 29.0

-10.5 -35.2 -30.5 - -2.2

19 22 48

19 - 2

TABLE 3

  Note: * 6) * 7) * 8) We We use us utility us * 9) As the term replaced is chlorotrifluoroethylene dichlorodifluoroethylene is vinylidene fluoride note * 5) of table 1, except that "fluoroalkyl acrylate" t must be

with "-1 fluorinated olefin".

  Monomers used (parts) Butadiene Acrylonitrile "-fluorinated olefin Example 6 40 35 25 * 6) Example 7 45 45 10 * 6) Example 8 30 20 50 * 6) Example 9 25 20 557)

Example

  comparative 9 60 40 O "c 60 35 5 * 6) il" 11 35 10 55 * 6) t '12 40 50 10 * 6)

13 45 30 25 * 8)

  TABLE 3 (continued) Tert-dodecanethiol Conversion of Mooney Consistency (parts) polymerization1 + 4 c) TO _ (, final (%) 1, + 4 '100 OC)

0.7 58.1 80

1.0 90.3 58

0.8 60.0 85

_. _.

0.7 58.5 88

0.33 71.0 70

0.45 68.0 56

0.5 56.2 40

_, _ ,,,,,

1.0 58.2 70

0.7 59.5 83

  TABLE 3 (continued) Composition of the copolymer (5 molar) * 9) Temperature of Butadine Acrylonitrile f-oleene intense transition ___ __, _ _ f luoréee, _, _ ,, _ ,,, _,, _,

61.3 33.3 5.4 - -32

* 1

62.0 3457 3.3 -34

63.2 25.3 11.5 -37

59.3 25.9 14.8 -33

59.5 40.5 0 -22

66.0 33.3 0.7 -38

77.4 6.0 16.6 -48

.9 46.7 2.4 -10

.7 25.8 8.5 -55

TABLE 4

  Example 6 Example 7 Example 8 Characteristics of the vulcanizate Tensile strength (daN / cm) 134 115 136 Elongation (%. 460 420 480 Hardness (JISA) 68 66 64 Resistance to petrol containing alcohol

(%) 55.2 59.7 50.2

  Resistance to acid gasoline Elongation at the Pas de Pas de Pas cracking (%) fissura-- fissura- -fissuration tion Elongation at break (%) 270 250 290 Resistance to solvent Fuel C 33.1 33:, 0 38.2 AV after immersion at 40 C for 48 h (%) Permanent deformation by compression

24 23 18

  (120 OC x 70 h) 24 23 18 Temperature resistant at low temperature -24.5 27.0 -29.0 Fragility test with cdoc (C)

_.__ _ _,.,., _. __ ,, _ _ _,.,

  TABLE 4 (continued) Ex l9ExampleExample Example Comparative example 9 comparative 10 comparative 11

128 134 124 99

473,460 460,410

63 63. 63 63

48.1 76 80.4 99

  No 50 85 No cracking cracking

305 160 185 205

t

37.1 39 47.2 87

17 24 23 15

-26.0 -24.2 -32.6 -45

  TABLE 4 (continued) Example Comparative example 12 comparative 13

134,124

390,350

71 68

59.0 64

No cracking

180

, 2 50

31 25

-10.5 -37.8

R E V E N D CATI 0 NS

  1 - Polymeric rubber with several components comprising (A) 15 to 60 moles I of a nitrile, P-unsaturated, (B) 10 to 75 moles% of a conjugated diene and (C) 2 to 55 moles% of a fluoroalkyl acrylate or methacrylate, t -ole-

  fine fluorinated or a combination of the two and having a temperature

  glass transition rature (T) from -50 C to -20 C, the percentages of components (A), (B) and (C) being expressed relative to the total sum of the moles of components (A), (B)

and (C).

  2 - Multicomponent polymer rubber according to Claim 1, in which the component (A) is

1t 'acrylonitrile.

  3 - Polymeric rubber with several components se-

  lon one of claims 1 or 2, wherein the component

(B) is 1,3-butadiene.

  4 - Polymeric rubber with several components se-

  lon claim 1, wherein component (C) is a

  fluoroalkyl acrylate or methacrylate whose radical al-

  kyle has 1 to 15 carbon atoms.

  - Multi-component polymer rubber se-

  lon claim 4, wherein the acrylate or methacry-

  fluoroalkyl late is 1,1- acrylate or methacrylate

  dihydroperfluoroethyl or 1,1- acrylate or methacrylate

dihydroperfluoropropyl.

  6 - Polymeric rubber with several components se-

  claim 1, wherein component (C) is chlorotrifluoroethylene, dichlorodifluoroethylene or one of

their mixtures.

  7 - Polymeric rubber with several components se-

  lon claim 4, wherein the proportions of the compounds

  sants (A), (B) and (C) are respectively 20-45 mole% o

-70 mole% and 2-35 mole%.